CN112714612A - Compositions comprising PVA and certain herbicides with improved properties - Google Patents

Compositions comprising PVA and certain herbicides with improved properties Download PDF

Info

Publication number
CN112714612A
CN112714612A CN201980059551.6A CN201980059551A CN112714612A CN 112714612 A CN112714612 A CN 112714612A CN 201980059551 A CN201980059551 A CN 201980059551A CN 112714612 A CN112714612 A CN 112714612A
Authority
CN
China
Prior art keywords
component
combination
total amount
alkyl
combination according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201980059551.6A
Other languages
Chinese (zh)
Other versions
CN112714612B (en
Inventor
L·洛伦兹
R·德克尔
S·萨绍
U·比克斯
M·泰尔舍
A·卡兹米尔恰克
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of CN112714612A publication Critical patent/CN112714612A/en
Application granted granted Critical
Publication of CN112714612B publication Critical patent/CN112714612B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/24Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients to enhance the sticking of the active ingredients
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to the technical field of crop protection. More particularly, the present invention relates to a combination of (I) polyvinyl alcohol (PVA) and (II) a composition comprising one or more water-soluble herbicidal active ingredients and certain other components, which combination has improved properties, in particular with respect to rain-fastness and/or herbicidal efficacy. The invention also relates to the use of such a combination.

Description

Compositions comprising PVA and certain herbicides with improved properties
Technical Field
The present invention relates to the technical field of crop protection. More particularly, the present invention relates to a combination of (I) polyvinyl alcohol (PVA) and (II) a composition comprising one or more water-soluble herbicidal active ingredients and certain other components, which combination has improved properties, in particular with respect to rain-fastness and/or herbicidal efficacy. The invention also relates to the use of such a combination.
Background
Crop protection agent compositions can be formulated in many different ways, wherein the nature of the active ingredient and the properties of the formulation may cause problems in terms of stability, efficacy and applicability of the formulation. Moreover, certain formulations are more advantageous than others for economic and environmental reasons.
Water-based formulations generally have the advantage that they require a low proportion of organic solvents, or are not required at all. On the other hand, the distribution of the components in such formulations is often inadequate unless a suitable combination of adjuvants is used. The performance of such formulations is generally dependent on a large number of variable parameters, and if the resulting formulation is biologically active, stable on storage and desirable from an application point of view, it is not possible to simply select the components of the known system and combine it with the active ingredient intended for the new formulation.
Rain resistance refers to the ability of an insecticide (insecticide formulation) to withstand rainfall and maintain biological efficacy to a high degree. For most insecticides, rain immediately after application will remove most of the insecticide residue from the leaf surface. Products that remain on the leaf surface in higher proportions after rain allow even more insecticide to penetrate the leaves and provide weed control activity.
An insecticide is considered "rain-tolerant" after application if it is sufficiently dry, physically retained on the leaf surface, or has been absorbed by plant tissue, and thus is still effective after rainfall or irrigation.
The degree of rain resistance depends on many factors. Most important is rain water. All pesticide products require a certain amount of drying time between application and rainfall.
Some pesticide products are designed with adjuvants, which are materials added to the formulation to increase efficacy. Some adjuvants improve rain tolerance by enhancing the ability of the active ingredient to penetrate into the leaf or bind to the plant/leaf surface, and still have sufficient selectivity in herbicide tolerant crops.
Post-emergence herbicides are applied to weeds that have already emerged, an example being glyphosate. Traditional formulations of glyphosate require a drying period of 6-12 hours after application. Rainfall or irrigation during this period will reduce efficacy and require a second application.
Therefore, standard formulations are rarely suitable to meet specific requirements, and therefore extensive experimental work must be involved to develop a suitable formulation. Many herbicidal formulations comprising water-soluble active crop protection agent ingredients have been described.
Examples of herbicidal formulations comprising glufosinate-ammonium and certain surfactants are known from US 4,400,196.
US 5,152,823 discloses aqueous insecticides based on active substance-containing dispersions in combination with water-soluble active substances and comprising as surfactant a combination of an alkyl ether sulfate with an ethoxylated fatty alcohol and a sulfosuccinate monoester.
US 5,258,358 mentions liquid herbicidal compositions comprising glufosinate-ammonium salts and alkylpolyglycosides, optionally in combination with certain other surfactants.
US 5,332,714 relates to low foaming concentrated liquid aqueous formulations of plant protection agents comprising sulfate or sulfonate containing surfactants as wetting agents and certain other surfactants as defoamers.
WO 92/12637 discloses improved dry and water soluble glyphosate formulations.
US 6,713,433 teaches a liquid concentrate herbicidal emulsion composition comprising a water-soluble herbicide, an oil-soluble herbicide, a stabilizing amount of a water-soluble chloride, and one or more surfactants.
US 2005/0266999 and US 8,110,529 relate to concentrated aqueous formulations for crop protection comprising certain types of surfactants and ammonium or aluminium silicates.
WO 2007/092351 discloses stable concentrate compositions comprising a water-soluble herbicide ingredient, an alkyl ether sulphate, an organic solvent and an alkyl polyglycoside.
US 8,901,041 discloses low-foaming aqueous formulations for crop protection comprising anionic surfactants and specific silicone-based antifoams.
WO 2004/105916 relates to an aqueous concentrate composition comprising an agrochemical, one or more foam-initiating surfactants and a defoamer, wherein the defoamer is incorporated into the composition as a solution in an organic solvent.
ACS appl. mater. interfaces 2016,8, 14220-.
US 2,510,839 discloses an improved composition comprising 2,4-D petroleum oil of a specific viscosity and different sulfonates.
US 4,954,497 relates to certain acrylic morpholines which show excellent fungicidal effects even after rainfall after spraying over the known compounds.
WO 95/16351 and WO 97/00010 relate to surfactants that provide enhanced efficacy and/or rain-fastness to pesticide formulations.
US 9,374,996 provides a pesticide composition comprising a copolymer of acrylic acid, poly (alkylene glycol) (meth) acrylate and alkyl (meth) acrylate, which has high rain resistance and/or pesticide retention.
US 5,491,125 teaches liquid herbicidal compositions comprising glufosinate in combination with certain types of surfactants and low levels of organic solvents, which have improved herbicidal activity, high low temperature stability and rain resistance.
Disclosure of Invention
In view of these known formulations, it is an object of the present invention to provide combinations comprising one or more water-soluble active herbicidal ingredients which have improved properties, in particular improved rain resistance and/or herbicidal properties.
It has been found that a combination of polyvinyl alcohol and a composition of water-soluble active herbicidal ingredients comprising certain surfactants, wherein the combination preferably additionally comprises certain esters, has such improved properties, in particular improved rain-fastness and/or herbicidal properties.
Accordingly, the present invention relates primarily to a combination comprising or consisting of:
(I) one or more kinds of polyvinyl alcohol(s),
(II) a composition comprising or consisting of:
(a) one or more water-soluble, herbicidally active crop protection agent components (active ingredients of type (a)),
(b) one or more C6-C16Fatty alcohol polyglycol ether sulfate and/or C6-C16Alkyl polyglycoside and/or C10-C18The fatty alkylamine ethoxylates are described as being fatty alkyl amines ethoxylates,
wherein the ratio of the total amount of component (I) to the total amount of component (II) is from 1:100 to 1:5, based on the total weight of the combination.
It has been found that the combination according to the invention shows improved properties, in particular improved rain resistance and/or herbicide resistance, as a result of the combination of components (I) and (II) as defined in the context of the invention.
In such a combination, the preferred ratio of polyvinyl alcohol of component (I) to the total weight of component (II), i.e. the defined composition used according to the invention, is in each case 1:100 to 1:5, preferably 1:50 to 1:10, more preferably 1:40 to 1:10, even more preferably 1:30 to 1:12, based on the total weight of the combination.
Such combinations may be in the form of kits, co-packages (suitable or recommended for tank mixes), or tank mixes. In the context of the present invention, the co-package is preferably a double package or a triple package.
In the context of the present invention, the polyvinyl alcohol used as component (I) in combination with component (II) in the combination according to the invention is preferably a partially hydrolyzed polyvinyl acetate having a degree of hydrolysis of from 75 to 97 mol-%, more preferably a degree of hydrolysis of from 80 to 95 mol-%, even more preferably a degree of hydrolysis of from 84 to 92 mol-%.
The polyvinyl alcohol used as component (I) preferably has a degree of polymerization of 150-1000, more preferably 250-750, and even more preferably 250-500.
The viscosity of a 4% by weight aqueous solution of the polyvinyl alcohol used as component (I) [20 ℃ C. according to DIN 53015: 2001-02 (published 2001-02) (viscosity measured by roller ball viscometer) ] is preferably 3 to 50mPas, more preferably 3.5 to 10mPas, even more preferably 3.5 to 6 mPas.
Such polyvinyl alcohols are commercially available, for example from Kuraray
Figure BDA0002971463940000041
Product range.
Generally and preferably, the composition used as component (II) in the context of the present invention is liquid at 25 ℃ and 1013 mbar.
In The context of The present invention, The water-soluble, herbicidally active Crop Protection agent components and further herbicidally active Crop Protection agent components of component (a) of The composition used as component (II) as well as The herbicide safeners of optional component (h) of The combination of The invention (preferably of The composition used as component (II) in The context of The present invention) and The generic names used herein are well known, see for example "The Pesticide Manual", 16 th edition, British Crop Protection Council 2012; these include known stereoisomers (particularly racemic and enantiomerically pure isomers) and derivatives such as salts or esters, particularly in the form which is customary commercially.
In the context of the present invention, the water-soluble herbicidally active crop protection agent component (active component type (a)) has a water solubility of at least 5g/l or more, preferably of at least 10g/l or more, more preferably of at least 20g/l or more at 20 ℃ and 1013mbar (depending on the form, generally in the pH range of 4 to 7).
In order to allow high concentrations of the water-soluble herbicidally active crop protection agent ingredient(s) (active ingredient type (a)) in the compositions to be used as component (II) in the context of the present invention, they are preferably used in the form of their salts, since these generally exhibit a relatively high water solubility.
The compositions used as component (II) in the context of the present invention preferably comprise as component (a) one or more water-soluble active crop protection agent ingredients selected from glufosinate-ammonium [ 2-amino-4- [ hydroxy (methyl) phosphono ] butanoic acid ] and salts thereof, glyphosate [ N (phosphonomethyl) glycine ] and salts thereof, MCPA [ (4-chloro-2-methylphenoxy) acetic acid ] and salts thereof, dicamba [3, 6-dichloro-2-methoxybenzoic acid ] and salts thereof, 2,4-D [2, 4-dichlorophenoxy) acetic acid ] and salts thereof and dipropionic acid [2- (2, 4-dichlorophenoxy) propionic acid ] and salts thereof.
The compositions used as component (II) in the context of the present invention preferably comprise as component (a) one or more water-soluble active crop protection agent ingredients selected from the group consisting of: glufosinate-ammonium salt, glufosinate-sodium salt, L-glufosinate-ammonium salt, L-glufosinate-sodium salt, glyphosate-diammonium salt, glyphosate-dimethylammonium salt, glyphosate-isopropylammonium salt, glyphosate-monoammonium salt, glyphosate-potassium salt, glyphosate-dipotassium salt, glyphosate-sesquisulfonate sodium salt (N- (phosphonomethyl) glycine sodium salt (2:3)), glyphosate trimethylsulfonium salt, MCPA-dimethylammonium salt, MCPA-diethanolamine, MCPA-alkanolamine, MCPA-potassium salt, MCPA-sodium salt, MCPA-triethanolamine, dicamba-dipropylamine, dicamba-diglycolamine, dicamba-dimethylammonium salt, dicamba-diethanolamine, dicamba-isopropylammonium salt, dicamba-ethanolamine, Dicamba-potassium salt, dicamba-sodium salt, dicamba-triethanolamine, dicamba-choline, dicamba-BAPMA (N, N-bis- (3-aminopropyl) methylamine), 2, 4-D-ammonium salt, 2, 4-D-choline, 2,4-D-BAPMA (N, N-bis- (3-aminopropyl) methylamine), 2, 4-D-diethylammonium salt, 2, 4-D-dimethylammonium salt, 2, 4-D-dialkanolamine, 2, 4-D-dodecylammonium salt, 2, 4-D-heptylammonium salt, 2, 4-D-isopropylammonium salt, 2, 4-D-lithium salt, 2, 4-D-potassium salt, 2, 4-D-sodium salt, dicamba-choline, dicamba-BAPMA (N, N-bis- (3-aminopropyl) methylamine), 2, 4-D-tetradecylammonium salt, 2, 4-D-triethylammonium salt, 2, 4-D-tris (2-hydroxypropyl) ammonium salt, 2, 4-D-triethanolamine, dipropionic acid-dimethylammonium salt, dipropionic acid-ethylammonium salt, dipropionic acid-potassium salt, and dipropionic acid-sodium salt.
Particularly preferably, component (a) of the composition used as component (II) in the context of the present invention comprises or consists of: glufosinate-ammonium, glufosinate-sodium, L-glufosinate-ammonium, L-glufosinate-sodium, glyphosate-potassium, glyphosate-ammonium, glyphosate-dimethylammonium, glyphosate-isopropylammonium, glyphosate-trimethylsulfonium (sulfoglufosinate), dicamba-diglycolamine, dicamba-BAPMA and 2, 4-D-choline.
Component (b) of the compositions used as component (II) in the context of the present invention is a group of surfactants known in the art to allow good stability and/or activity of the compositions comprising water-soluble, herbicidally active crop protection agent ingredients ((a) type active ingredients).
C of component (b) of the composition used as component (II) in the context of the present invention6-C16The fatty alcohol polyglycol ether sulfate preferably corresponds to the formula CH3(CH2)m(OCH2CH2)nOSO3M, wherein M is a cation, M represents an integer from 4 to 15, and n is 2, 3,4 or 5.
Preferably, M is selected from Na+、K+Or NH4 +M represents an integer from 6 to 15 and n is 2, 3,4 or 5.
More preferably, M is selected from Na+、K+Or NH4 +M represents an integer from 9 to 15 and n is 2, 3,4 or 5.
A more preferred fatty alcohol polyglycol ether sulfate as component (b) is C10-C16Fatty alcohol diethylene glycol ether sulphate (i.e. n is 2).
C of component (b) as defined in the composition of the invention as component (II)6-C16The alkyl polyglycoside is preferably C6-C16Alkyl polyglucoside, more preferably C8-C12Alkyl polyglucosides.
C suitable as component (b)6-C16Alkyl polyglycosides, especially C6-C16Alkyl polyglucosides are known in the art and are commercially available, for example, alkyl polysaccharides and mixtures thereof, e.g. from
Figure BDA0002971463940000071
Those of series (Croda), with or without addition of inorganic salts (such as ammonium sulphate); agnique from BASF
Figure BDA0002971463940000072
Alkyl polyglycosides in a graded form, e.g.
Figure BDA0002971463940000073
PG 8107 (fatty alcohol C)8-C10Glucoside) glucoside(s),
Figure BDA0002971463940000074
PG 9116 (fatty alcohol C)9-C11Glucoside), based on C8-C10Alkylpolyglycoside/alkylpolysaccharide mixtures of fatty alcohols, e.g.
Figure BDA0002971463940000075
225DK and
Figure BDA0002971463940000076
215CSUP(BASF)。
c of component (b) of the composition used as component (II) in the context of the present invention10-C18The fatty alkylamine ethoxylates preferably correspond to the formula H (OCH)2CH2)pN(R6)(CH2CH2O)qH, wherein R6Is represented by C10-C18Alkyl, p represents an integer of 1 to 10, and q represents an integer of 1 to 10.
Preferably, R6Is represented by C12-C18Alkyl, p represents an integer of 1 to 8, and q represents an integer of 1 to 8.
More preferably, R6Is represented by C12-C16Alkyl, p represents an integer of 1 to 6, and q represents an integer of 1 to 6.
More preferably, the context of the present inventionComponent (b) of the composition of (a) to (II) comprises or consists of: one or more C10-C16Fatty alcohol diethylene glycol ether sulfate and/or C with polymerization degree less than 58-C12Alkyl polyglucosides, and/or C having 2 to 10 Ethylene Oxide (EO) units12-C16An alkylamine ethoxylate.
Particularly preferably, component (b) of the composition used as component (II) in the context of the present invention comprises or consists of: one or more C12-C14Fatty alcohol diethylene glycol ether sulfate sodium salt, potassium salt, ammonium salt (preferably sodium salt) and/or C with polymerization degree less than 28-C10Alkyl polyglucosides and/or C having 4 to 8 Ethylene Oxide (EO) units12-C14Alkylamine ethoxylates [ preferably ethoxylated 3-isotridecyloxypropylamine (CAS number 68478-96-6; system name: poly (oxy-1, 2-ethanediyl),. alpha.' - [ [3- (tridecyloxy) propyl ]]Imino radical]Bis-2, 1-ethanediyl]Bis [. omega. -hydroxy-, branched)]。
In the compositions used as component (II) in the context of the present invention, wherein glufosinate-ammonium salt is (part of) component (a), it is preferred that component (b) comprises one or more C as defined above10-C16Fatty alcohol diethylene glycol ether sulfate and/or C8-C12Alkyl polyglucosides, preferably as defined in one of the preferred or more preferred embodiments.
In the context of the present invention, compositions for use as component (II) wherein one of the above glyphosate salts is part of component (a), preferred component (b) comprises or consists of a C as defined above8-C12Alkyl polyglucosides and/or C having 2 to 10 Ethylene Oxide (EO) units12-C16Alkylamine ethoxylate composition, preferably as defined in one of the preferred or more preferred embodiments.
C as (part of) component (b) of the present invention6-C16The fatty alcohol polyglycol ether sulphate has the advantage that the amount of component (c) which can be incorporated in the composition according to the invention is higher, thereby allowing further improved rain resistance and rain resistance of the compositionAnd/or herbicidal activity.
Preferably, the combination or component (II) according to the invention comprises one or more further components selected from components (c) to (h):
(c) one or more esters selected from (c1) - (c 3):
(c1)R1COOR2wherein R is1Is represented by C5-C13Alkyl and R2Is represented by C6-C14Alkyl radical, wherein R1And R2The total number of carbon atoms taken together is an integer from 14 to 22,
(c2)R3OOC-(CH2)x-COOR4wherein R is3And R4Independently of one another represent C4-C12Alkyl, and x is an integer from 1 to 6,
(c3)(R5O)3p ═ O, wherein R5Independently of one another represent C4-C16Alkyl radical, wherein three R5The total number of carbon atoms taken together is an integer from 18 to 42,
(d) an organic solvent, and a solvent mixture comprising an organic solvent,
(e) the amount of water is controlled by the amount of water,
(f) other surface-active agents which are capable of forming a hydrophilic,
(g) other adjuvants of the preparation can be added into the preparation,
(h) one or more further herbicidally active crop protection agent components and/or herbicide safeners.
The (preferred) components (c) to (h) optionally present in combination according to the invention are the same as the (preferred) components (c) to (h) detailed below for the composition used as component (II) in the context of the present invention. Preferably, components (d) to (h) are part of a composition used as component (II) in the context of the present invention, and in a preferred embodiment, components (c) to (h) are part of a composition used as component (II) in the context of the present invention.
Component (c), which is preferably part of the composition used as component (II) in the context of the present invention, is a group of esters defined by components (c1), (c2) and (c3) having the following structures.
Component (c1) in the context of the present invention has the following structure:
Figure BDA0002971463940000091
wherein R is1And R2Each represents the corresponding group as defined herein.
Component (c2) in the context of the present invention has the following structure:
Figure BDA0002971463940000092
wherein R is3、R4And x each have the corresponding meaning as defined herein.
Component (c3) in the context of the present invention has the following structure:
Figure BDA0002971463940000093
wherein each R5Represent the corresponding groups as defined herein.
The esters used as component (c), preferably as part of the composition used as component (II) in the context of the present invention, may be prepared by any method known in the art, for example by reacting the corresponding acid or acid halide moiety with the corresponding alcohol R2OH、R3OH、R4OH or R5And (5) OH esterification. Many esters of component (c) of the composition according to the invention are commercially available.
In the context of components (c1), (c2) and (c3) of component (c), which are preferably used as part of the composition of component (II) in the context of the present invention, the preferred alkyl radicals, i.e.R1、R2、R3、R4And R5Are each straight-chain and branched alkyl radicals, and are preferably selected from the group consisting of 1-butyl, 2-butyl, isobutyl, tert-butyl, 1-pentyl, 2-pentyl, isopentyl, 1-hexyl, 2-hexyl, isohexyl, 1-heptyl, 2-heptyl, isoheptyl, 1-octyl, 2-octyl, isooctyl, 2-ethylhexyl, 3,5, 5-trimethylhexyl, 3,4, 4-trimethylpentyl, 1-nonyl, 2-nonyl, isononyl, 1-decyl, 2-decyl, isodecyl2-propylheptyl, 1-dodecyl, 2-dodecyl and isododecyl. In the context of components (c1), (c2) and (c3) according to the invention, more preferred alkyl radicals R1、R2、R3、R4And R5Are branched alkyl groups, each preferably selected from the following: 2-hexyl, isohexyl, 2-heptyl, isoheptyl, 2-octyl, isooctyl, 2-ethylhexyl, 3,5, 5-trimethylhexyl, 3,4, 4-trimethylpentyl, 2-nonyl, isononyl, 2-decyl, isodecyl, 2-dodecyl and isododecyl.
Preferably, component (c), which is preferably part of the composition used as component (II) in the context of the present invention, comprises or consists of one or more esters selected from (c1) to (c 3):
(c1)R1COOR2wherein R is1Is represented by C7-C9Alkyl and R2Is represented by C8-C10Alkyl radical, wherein R1And R2The total number of carbon atoms taken together is an integer from 16 to 20,
(c2)R3OOC-(CH2)x-COOR4wherein R is3And R4Independently of one another represent C6-C10Alkyl, and x is an integer from 2 to 5,
(c3)(R5O)3p ═ O, wherein R5Independently of one another represent C6-C12An alkyl group.
More preferably, component (c), which is preferably part of a composition used as component (II) in the context of the present invention, comprises or consists of one or more esters selected from (c1) - (c 3):
(c1)R1COOR2wherein R is1C representing a branch7-C9Alkyl and R2C representing a branch8-C10Alkyl radical, wherein R1And R2The total number of carbon atoms taken together is an integer from 16 to 20,
(c2)R3OOC-(CH2)x-COOR4wherein R is3And R4Independently of one another, C of a branched chain6-C10Alkyl, preferably each 2-ethylhexyl, and xIs an integer of 2 to 5, and,
(c3)(R5O)3p ═ O, wherein R5Independently of one another, C of a branched chain6-C12An alkyl group.
Even more preferably, component (c), which is preferably part of a composition used as component (II) in the context of the present invention, comprises or consists of one or more esters selected from (c1) - (c 3):
(c1)R1COOR2wherein R is1Represents a branched chain C8Alkyl and R2Represents a branched chain C9An alkyl group, a carboxyl group,
(c2)R3OOC-(CH2)x-COOR4wherein R is3And R4Independently of one another, represents a branch C8Alkyl, preferably each 2-ethylhexyl, and x is 2, 3 or 4,
(c3)(R5O)3p ═ O, wherein R5Independently of one another, represents a branch C8An alkyl group.
Preferably, from a practical point of view and for reasons of (synthetic and/or commercial) availability, in the compositions used as component (II) in the context of the present invention, in component (c2), R is preferred3And R4All represent the same alkyl group, and in component (c3), all three R5All represent the same alkyl group.
In its own experiments, the following component (c) provides compositions which are used as component (II) in the context of the present invention with particularly improved properties. Thus, preferably, component (c), which is preferably part of the composition used as component (II) in the context of the present invention, comprises or consists of one or more esters selected from the group consisting of:
(c1)3,5, 5-trimethylhexanoic acid 3,5, 5-trimethylhexanoate, 7-methyloctanoic acid 7-methyloctanoate,
(c2) bis (2-ethylhexyl) adipate, bis (2-ethylhexyl) succinate; and
(c3) tris (2-ethylhexyl) phosphate.
For example, it has been found that the above-mentioned improved properties of the compositions used as component (II) in the context of the present invention are observed when component (c) comprises or consists of component (c2) when glyphosate salt is used as component (a). For example, improved rain resistance is especially observed when bis (2-ethylhexyl) adipate is used as component (c 2).
For example, it has also been found that the above-mentioned improved properties of the composition used as component (II) in the context of the present invention are observed when component (c) comprises or consists of component (c1) or (c3) when glufosinate is used as component (a). For example, improved rain resistance is especially observed when isononyl isononanoate and/or 3,5, 5-trimethylhexyl 3,5, 5-trimethylhexanoate is used as component (c1) or when tris (2-ethylhexyl) phosphate is used as component (c 3).
Preferred according to the invention are compositions for use as component (II) in the context of the present invention, wherein the weight ratio of the total amount of component (a) to the total amount of component (b) is from 10:1 to 1:6, and preferably from 8:1 to 1: 3.
Preferably, the weight ratio of the total amount of component (a) to the total amount of component (c) in the combination of the invention or in the composition used as component (II) in the context of the present invention is from 60:1 to 2:1, and preferably from 40:1 to 3: 1.
Preference is given to combinations according to the invention in which the weight ratio of the total amount of polyvinyl alcohol of component (I) to the total amount of component (c) contained in the combination is from 5:1 to 1:5, preferably from 3:1 to 1:3, more preferably from 2:1 to 1:2, in each case based on the total weight of the combination.
The optimum ratio range of component (a) to components (b) and (c) in the compositions used as component (II) in the context of the present invention depends to some extent on the water-soluble herbicidally active crop protection agent ingredients used and the amounts thereof contained in the composition.
For example, in compositions for use as component (II) in the context of the present invention wherein glufosinate-ammonium salt is part of component (a), the total amount of component (a) is preferred
The weight ratio of the component (b) to the total amount of the component (b) is 3:2-1:6,
and/or
The weight ratio of the component (c) to the total amount of the component (c) is 25:1 to 2: 1.
More preferably, in compositions for use as component (II) in the context of the present invention wherein glufosinate-ammonium salt is part of component (a), the total amount of component (a) is
The weight ratio of the component (b) to the total amount of the component (b) is 1:1-1:3,
and/or
The weight ratio of the component (c) to the total amount of the component (c) is 10:1-3: 1.
For example, in compositions for use as component (II) in the context of the present invention wherein one of the above-mentioned glyphosate salts is part of component (a), the total amount of component (a) is preferred
The weight ratio of the component (b) to the total amount of the component (b) is 8:1-1:1,
and/or
The weight ratio of the component (c) to the total amount of the component (c) is 25:1 to 4: 1.
More preferably, in compositions for use as component (II) in the context of the present invention wherein one of the above mentioned glyphosate salts is part of component (a), the total amount of component (a) is
The weight ratio of the component (b) to the total amount of the component (b) is 7:1-2:1,
and/or
The weight ratio of the component (c) to the total amount of the component (c) is 20:1 to 5: 1.
In a preferred embodiment, the combination according to the invention is a tank mix obtainable or obtained by mixing a combination as defined herein, preferably in one of the preferred embodiments, with water as component (III), wherein the weight ratio of the total amount of component (III) in the tank mix to the total amount of the combination as defined herein, preferably in one of the preferred embodiments, is from 1000:1 to 10:1, preferably from 500:1 to 25:1, more preferably from 400:1 to 50: 1.
Suitable organic solvents for use as component (d) of the composition of component (II) in the context of the present invention are different from component (c) and are preferably water-miscible organic solvents, examples being
Aliphatic alcohols, such as lower alkanols, such as, for example, methanol and ethanol or polyols, such as ethylene glycol and glycerol,
polar ethers such as alkylene glycol monoalkyl and dialkyl ethers such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monomethyl or monoethyl ether, diethylene glycol, hexanediol, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether;
amides such as dimethylformamide, dimethylacetamide, dimethyloctanoylamide, dimethyldecanoylamide and N-alkylpyrrolidones.
Preference is given here to organic solvents which are predominantly miscible with water. Preferably, component (d) comprises or consists of propylene glycol monomethyl ether, dipropylene glycol and/or propylene glycol, and preferably comprises or consists of 1-methoxy-2-propanol and/or dipropylene glycol.
Preferably, the composition used as component (II) in the context of the present invention comprises a total amount of from 0 wt% to 15 wt%, based on the total weight of the composition, of component (d). However, the total amount of component (d) in the compositions used as component (II) in the context of the present invention depends inter alia on the water-soluble herbicidally active crop protection agent ingredient present as (part of) ingredient (a), i.e. the active ingredient of type (a).
For example, in compositions used as component (II) in the context of the present invention, in which glufosinate ammonium salt is (part of) component (a), the preferred total weight of component (d) is 5 to 15 wt. -%, preferably 7 to 12 wt. -%, in each case based on the total weight of the composition. These amounts are particularly applicable when the glufosinate ammonium salt is (part of) component (a) and component (d) comprises or consists of propylene glycol monomethyl ether, dipropylene glycol and/or propylene glycol, and preferably comprises or consists of 1-methoxy-2-propanol and/or dipropylene glycol.
For example, in compositions for use as component (II) in the context of the present invention in which glyphosate salt is part of component (a), the preferred total weight of component (d) is from 0% to 5% by weight, preferably 0% by weight, in each case based on the total weight of the composition (i.e. without the organic solvent of component (d)).
The organic solvent used as component (d) of the composition of component (II) in the context of the present invention should only be used in an amount such that the aqueous phase is stable, preferably in the form of a thermodynamically stable aqueous solution.
The compositions used as component (II) in the context of the present invention may optionally comprise as component (f) further surfactants (anionic, cationic or zwitterionic and/or nonionic surface-active compounds (surfactants)) which do not belong to group (b) of the compositions used as component (II) in the context of the present invention, which can further contribute to improved stability, further improved availability of the plants or further improved activity of the water-soluble, herbicidally active crop protection agent components (active ingredients of type (a)).
As component (g), the compositions used as component (II) in the context of the present invention may comprise customary formulation auxiliaries, for example inert materials, such as binders, wetting agents, dispersants, emulsifiers, penetrants, preservatives, inorganic salts, stabilizers, antifreezes, fillers, carriers and colorants, evaporation inhibitors and pH regulators (buffers, acids and bases), viscosity regulators (e.g. thickeners) or defoamers. It may be advantageous to add inorganic salts, preferably ammonium salts such as ammonium chloride or ammonium sulfate, in particular with certain surfactants or with polyvinyl alcohol (see below).
Due to the presence of component (b), it is often advantageous to include a defoamer as (part of) component (g) of the present invention. Suitable antifoams include all customary antifoams, for example, preferably siloxane-based antifoams such as silicone oils. Silicone oils may also be used as emulsions.
The antifoam of the linear polydimethylsiloxane group comprises the formula HO- [ Si (CH)3)2-O-]nCompounds of the formula-H as their chemical backbone, in which the end groups are modified, for example by etherification, or are usually linked to the group-Si (CH)3)3. Preferred defoamers are defoamers selected from linear polydimethylsiloxanes, preferably comprising silica, in particular those mentioned in US 8,901,041. Silica encompasses a wide variety of forms/modifications, e.g. polysilicic acid, meta-silicic acid, orthosilicic acid, silica gel, silicic acid gel, diatomaceous earth, precipitated SiO2And the like.
Preferred according to the invention are compositions for use as component (II) in the context of the invention, wherein component (d) comprises or consists of propylene glycol monomethyl ether, dipropylene glycol and/or propylene glycol and preferably comprises 1-methoxy-2-propanol,
and/or
Component (f) comprises or consists of alkyl sulfosuccinate salts (diesters and monoesters)Composition, preferably comprising C6-C14Alkyl sulfosuccinate monoesters, more preferably lauryl ether-3 sulfosuccinate, in particular disodium lauryl ether-3 sulfosuccinate,
and/or
Component (g) comprises a defoamer, preferably a polydimethylsiloxane oil with silica gel.
Preferred according to the invention are compositions for use as component (II) in the context of the present invention, wherein component (d) comprises 1-methoxy-2-propanol, and wherein the composition preferably comprises polydimethylsiloxane oil (as part of component (g)) with silica gel as defoamer,
and
component (f) comprises or consists of alkyl sulfosuccinate salts (diesters and monoesters), preferably C6-C14Alkyl sulfosuccinate monoesters, more preferably lauryl ether-3 sulfosuccinate, especially disodium lauryl ether-3 sulfosuccinate.
As component (h), the compositions used as component (II) in the context of the present invention may comprise further herbicidally active crop protection agent ingredients (i.e. different from component (a)) and/or herbicide safeners. Preferably, such further herbicidally active crop protection agent components have a low water solubility of 1g/l or less, more preferably 0.5g/l or less at 20 ℃ and 1013mbar, preferably at pH 7. Preferred herbicide safeners of component (h) are cyprosulfamide, isoxadifen-ethyl, pyrazoline-diethyl, clethodim, fluprazole and toxquine.
In the case of compositions which are used as component (II) in the context of the present invention comprising as component (h) a further herbicidally active crop protection agent ingredient having low water solubility, i.e. different from component (a), it is preferred to comprise as part of component (f) or (g) one or more stabilizers.
Such stabilizers may be dispersing or suspending agents, for example selected from ionic polymers, for example sodium naphthalenesulfonate formaldehyde condensates or sodium Kraft-lignosulfonates, for example Morwet D245(Akzo Nobel) or Kraft perse 25M (Ingevity), or from nonionic polymers, for example polyethoxylated polymethacrylates, for example Atlox 4913 (Croda).
Such stabilizers may be dispersing or suspending agents, for example selected from ionic surfactants, for example sodium dialkylnaphthalene sulfates, such as Oparyl MT800(Bozetto), or non-ionic surfactants, for example tristyrylphenol alkoxylates, such as Soprophor 796/p (solvay), or block copolymers of ethylene/propylene oxide, such as Pluronic PE 6800 (BASF).
Such stabilizers may be selected from the group consisting of aluminum silicates, and may be mineral fibers, such as fibrous magnesium and aluminum silicate attapulgite, preferably
Figure BDA0002971463940000161
40(BASF) or
Figure BDA0002971463940000162
ATC (from CECA, Dusseldorf, Germany).
Figure BDA0002971463940000163
EWs (from Elementis) are also well suited, which likewise comprise hectorite as their base material.
The ingredients used to prepare and obtain the composition used as component (II) in the context of the present invention are known and many of these ingredients are commercially available.
The compositions used as component (II) in the context of the present invention are prepared by conventional methods by mixing and homogenizing the active ingredient (a) and all other components in solid or already dissolved form, if appropriate with stirring.
In a further aspect, the present invention relates to a process for the preparation of a combination according to the invention as defined herein, which comprises mixing components (I) - (II) and optionally water as component (III) and optionally other components present in the combination mentioned above and below in the context of the present invention.
In case components (f), (g) and/or (h) as defined herein are present in the composition used as component (II) in the context of the present invention and e.g. are poorly water soluble, it may be beneficial to include a grinding step, e.g. using a colloid mill or a stirred bead mill.
The compositions used as component (II) in the context of the present invention preferably exhibit good storage properties (i.e. storage stability, including low temperature stability), high bioavailability and thus retained activity of the water-soluble active crop protection agent ingredient, i.e. component (a).
The compositions used as component (II) in the context of the present invention are particularly suitable for crop protection for controlling undesired plant growth on uncultivated land and in crops which are resistant to one or more herbicides of component (a) used in the context of the present invention.
In a further aspect, the present invention relates to a method of controlling undesired plant growth, which comprises applying an effective amount of a combination according to the invention as defined herein to a plant, part of a plant or a cultivation area.
In a further aspect, the present invention relates to the use of a combination according to the invention as defined herein for controlling undesired plant growth.
Detailed Description
All amounts indicated hereinafter are weight percentages (wt. -%), unless otherwise indicated.
Abbreviations and products used (including trade names):
a.i. ═ of active ingredient (amount)
GFA ═ glufosinate-ammonium salt
GIPA-glyphosate-isopropylammonium salt
Figure BDA0002971463940000171
LRO paste ═ C12/C14Sodium salt of fatty alcohol diethylene glycol ether sulphate, used as a 70% wt. -% aqueous solution, (Clariant)
Figure BDA0002971463940000172
Isononyl isononanoate 99 (Nisshin Oillio)
POVALTM4-88 ═ polyvinyl alcohol (polyvinyl acetate with a degree of hydrolysis of about 88%) (Kuraray)
Figure BDA0002971463940000173
TOF tris- (2-ethylhexyl) phosphate (Lanxess)
DowanolTMPM ═ propylene glycol monomethyl ether (Dow)
Figure BDA0002971463940000174
482 dimethyl silicone defoamer with silica gel (Bluestar Silicones)
Figure BDA0002971463940000175
PG 8105=C8-C10Alkyl polyglycosides (used in 62-65wt. -% strength aqueous solution (BASF)
Figure BDA0002971463940000176
88A ═ Lignosulfonic acid, sodium salt, sulfomethylation (sodium salt of chemically modified Low molecular weight Kraft lignin Polymer solubilized by five sulfonate groups, DKSH)
Figure BDA0002971463940000177
NA ═ purified sodium lignosulfonate (Borregaard)
SynergenTM GA=C8-C10Alkylglucamides (used as 50% strength aqueous solutions, Clariant)
Figure BDA0002971463940000178
CP5 ═ copolymer of methacrylic acid and acrylic acid (used as a 40% strength aqueous solution, BASF)
Figure BDA0002971463940000179
M ═ myristamine oxide (used as a 25% strength aqueous solution, Stepan)
Table R1: reference formulation GFA SL196
Figure BDA00029714639400001710
Figure BDA0002971463940000181
Table R2: reference formulation GIPA51
Figure BDA0002971463940000182
Biological examples
The Growth stages of the different weed species are described in accordance with the BBCH monograph "Growth stages of mono-and dicotyledonous plants", second edition, 2001, editor Uwe Meier, Federal Biological Research Centre for Agriculture and forest (Biological Bunkastanbut fur Land und Forstwitschaft). The corresponding BBCH stages are described below for different weed species.
In tables 01 to 07 below, for reasons of comparability of the test results, the percentage content of each test compound is by weight and refers to the absolute content of each test compound used, i.e. any diluent (e.g. water) present in the commercial products indicated above with trade names is not reflected in said content. For example, if Ammonyx M (25% aqueous solution of myristamine oxide) is used, the amount of 3% indicated in the table is the amount of myristamine oxide (and corresponds to the amount of 12% commercial Ammonyx M).
Greenhouse rain resistance test: chenopodium album (CHEAL) and Lolium multiflorum (LOLMU) plants were grown in 7 cm pots in the greenhouse until the appropriate developmental stage was reached (provided in the different results tables) and applied after selection of uniform plants. 400g of a.i./ha GFA SL196 formulation and a mixture of different test compounds and GFA SL196 formulation in a ratio of 400g a.i./ha and 10% by weight of test compound were applied at a water application rate of 300L/ha to a test apparatus 002 flat fan nozzle linear orbit sprayers. Six groups of plants were treated with different test mixtures and a reference containing a GFA SL196 formulation, with each weed species containing 4 replicates. The first group received no irrigation after treatment, while the remaining 5 groups received 5.5L/m 2 hours after the initial herbicide treatment2Irrigation. Irrigation was applied on a linear track sprayer equipped with 8005 flat fan nozzles in series at 1.5 bar water pressure, providing 5.5mm of rain for each group of plants. On day 14 after application (14DAA), the different weed species were assessed visually on a percentage scale relative to untreated controls (100%: all plants dead; 50%: green plant biomass reduced by 50%, and 0%: no significant difference: similar control plots) (for chenopodium, see tables 01 and 02).
In the second rain resistance test, the conditions were similar except that the rate of GFA application was reduced to 350g a.i./ha GFA. The concentrations of the selected test compounds were reduced to 3wt. -% and 5wt. -%, respectively (table 03 chen).
In a further rain resistance test, glyphosate (used at 540g a.i./ha GIPA) was mixed with POVAL 4-88 in an amount of 5wt. -% to be tested (Chenopodium album Table 04).
Table 01: comparative test with glufosinate-ammonium salts (10 wt. -% of each test compound to 400g a.i./ha GFA) on Chenopodium plants (BBCH18-20) in a greenhouse rain assay
Figure BDA0002971463940000191
Table 02: test results on Chenopodium quinoa plants (BBCH18-20) with a composition according to the invention and glufosinate-ammonium salt (addition of 10wt. -% POVAL 4-88 to 400g a.i./ha GFA SL 196) in a greenhouse rain assay
Figure BDA0002971463940000201
Table 03: test results with the composition according to the invention and GFA (addition of 5 wt.% POVAL 4-88 and 3 wt.% Salacos 99 or Dislamell TOF to 350g a.i./ha GFA SL 196) on Chenopodium plants (BBCH 17-19) in a greenhouse rain assay
Figure BDA0002971463940000202
Table 04: test results on Chenopodium quinoa (CHEAL) plants (BBCH 17-19) in a greenhouse rain assay with a composition according to the invention and glyphosate (5 wt. -% POVAL 4-88 to 540g a.i./ha GIPA)
Figure BDA0002971463940000203
Field trials to evaluate weed control efficacy:
the compounds previously tested in the greenhouse and 350g of GFA a.i./ha were tested in the field, alone and in various combinations, to assess efficacy under field conditions. The sown weeds were applied in a replicated random whole block design. Test compounds were added to GFA SL196 formulation at a rate of 3% wt. -% and 5% wt. -%, respectively. The plots were sprayed with an application rate of 140L/ha and a hand-held spray bar. On day 14 after application (14DAA), the different weed species were assessed visually on a percentage scale relative to untreated controls (100%: all plants dead; 50%: green plant biomass reduced by 50%, 0%: no significant difference: similar control plots) (see table 05a, table 05b, table 06).
The effects on the following weeds (depending on the presence in each field) were evaluated: abutilon theophrasti (ABUTHON), Chenopodium quinoa (CHEAL), Avena sativa (Avena fatua, AVEFA), Chenopodium alpinum (Bassia scoparia, KCHSC) and Triticum aestivum (TRZAS).
Table 05 a: weed control efficacy of dicotyledonous weeds-compositions and glufosinate-ammonium salts were used in field trials to improve activity in field trials. At 350g a.i.GFA SL196+ Disfialloll TOF of the tank mix; salacos 99; tests were carried out in POVAL 4-88; BBCH codes are provided when applied.
Figure BDA0002971463940000211
(*): combinations not according to the invention
Table 05 b: weed control efficacy of monocotyledonous weeds (grasses) -the composition according to the invention and glufosinate-ammonium salt were used in field trials to improve activity in field trials. At 350g of a.i.GFA + Disfialloll TOF in the tank mix; salacos 99; tests were carried out in POVAL 4-88; BBCH codes are provided when applied.
Figure BDA0002971463940000221
(*): combinations not according to the invention
Table 06: weed control efficacy-comparative field test results of formulations and glufosinate-ammonium salts. The test was carried out on 350g of a.i.gfa +3wt. -% of each test compound of the tank mix; BBCH codes are provided when applied.
Figure BDA0002971463940000222
Field test to determine rain resistance:
wheat (TRZAS) plants in the growth phase of BBCH 23 were applied 350g a.i./ha GFA alone and in combination with 5wt. -% POVAL 4-88 as a GFA 196SL formulation. The plots were sprayed at 140L/ha application rates with a hand-held spray bar. After half of the treatment was applied for 1 hour, about 20L/m was irrigated2The water of (2). On day 14 after application (14DAA), the different weed species were assessed visually on a percentage scale relative to untreated controls (100%: all plants dead; 50%: green plant biomass reduced by 50%, and 0%: no significant difference ═ similar control plots) (see table 7).
Table 7: a field test to determine rain resistance of the compositions of the invention in wheat (TRZAS). The test was performed using 350g of a.i.gfa +5wt. -% POVAL 4-88 of the tank mix; BBCH codes are provided when applied.
Figure BDA0002971463940000231
In the following, preferred embodiments of component (II) for use in the combination according to the invention are described.
Embodiment 1. component (II) used in the combination according to the invention is preferably a composition comprising or consisting of:
(a) one or more water-soluble, herbicidally active crop protection agent components (active ingredients of type (a)),
(b) one or more C6-C16Fatty alcohol polyglycol ether sulfate and/or C6-C16Alkyl polyglycoside and/or C10-C18The fatty alkylamine ethoxylates are described as being fatty alkyl amines ethoxylates,
and optionally, one or more additional components selected from components (d) - (h):
(d) an organic solvent, and a solvent mixture comprising an organic solvent,
(e) the amount of water is controlled by the amount of water,
(f) other surfactants (i.e., different from component (b)),
(g) other formulation adjuvants (i.e., other than components (b) - (f)),
(h) one or more further herbicidally active crop protection agent components and/or herbicide safeners.
Embodiment 2 is a composition according to embodiment 1, comprising:
a total amount of 5-70% by weight of component (a),
a total amount of 5-60% by weight of component (b),
and optionally, one or more additional components selected from components (d) - (h):
a total amount of 0 to 15% by weight of component (d),
a total amount of 0.1-60% by weight of component (e),
a total amount of 0.1 to 30% by weight of component (f),
a total of 0.1% to 20% by weight of component (g),
a total of 0.1 to 20% by weight of component (h),
in each case based on the total weight of the composition.
Embodiment 3 is the composition according to embodiment 1 or embodiment 2, comprising:
a total amount of 10-60% by weight of component (a),
a total amount of 5-50% by weight of component (b),
a total amount of 20 to 60% by weight of component (e),
and optionally, one or more further components selected from components (d), (f), (g) and (h):
a total amount of 0 to 15% by weight of component (d),
a total amount of 0.1 to 20% by weight of component (f),
a total of 0.1-12% by weight of component (g),
a total of 0.1 to 12% by weight of component (h),
in each case based on the total weight of the composition.
Embodiment 4 is the composition of any one of embodiments 1-3, comprising as component (a) one or more active ingredients selected from glufosinate and salts thereof, glyphosate and salts thereof, MCPA and salts thereof, dicamba and salts thereof, 2,4-D and salts thereof, and dichlorprop and salts thereof.
Embodiment 5 is the composition of any one of embodiments 1-4, wherein component (a) comprises or consists of one or more active ingredients selected from the group consisting of: glufosinate-ammonium, glufosinate-sodium, L-glufosinate-ammonium, L-glufosinate-sodium, glyphosate-potassium, glyphosate-ammonium, glyphosate-dimethylammonium, glyphosate-isopropylammonium, glyphosate-trimethylsulfonium (sulfoglufosinate), dicamba-diglycolamine, dicamba-BAPMA and 2, 4-D-choline.
Embodiment 6 is the composition of any of embodiments 1-5, wherein component (b) comprises or consists of: one or more C10-C16Fatty alcohol diethylene glycol ether sulfate and/or C with polymerization degree less than 58-C12Alkyl polyglucosides, and/or C having 2 to 10 Ethylene Oxide (EO) units12-C16Alkylamine ethoxylationA compound (I) is provided.
Embodiment 7 is the composition of any of embodiments 1-6, wherein component (b) comprises or consists of: one or more C12-C14Fatty alcohol diethylene glycol ether sulfate sodium salt, potassium salt, ammonium salt and/or C with polymerization degree less than 28-C10Alkyl polyglucosides and/or C having 4 to 8 Ethylene Oxide (EO) units12-C14An alkylamine ethoxylate.
Embodiment 8 is the composition of any one of embodiments 1-7, further comprising component (c), wherein component (c) comprises or consists of one or more esters selected from (c1) - (c 3):
(c) one or more esters selected from (c1) - (c 3):
(c1)R1COOR2wherein R is1Is represented by C5-C13Alkyl and R2Is represented by C6-C14Alkyl radical, wherein R1And R2The total number of carbon atoms taken together is an integer from 14 to 22,
(c2)R3OOC-(CH2)x-COOR4wherein R is3And R4Independently of one another represent C4-C12Alkyl, and x is an integer from 1 to 6,
(c3)(R5O)3p ═ O, wherein R5Independently of one another represent C4-C16Alkyl radical, wherein three R5The total number of carbon atoms taken together is an integer from 18 to 42.
Embodiment 9 is the composition of embodiment 8, wherein component (c) comprises or consists of one or more esters selected from (c1) - (c 3):
(c1)R1COOR2wherein R is1Is represented by C7-C9Alkyl and R2Is represented by C8-C10Alkyl radical, wherein R1And R2The total number of carbon atoms taken together is an integer from 16 to 20,
(c2)R3OOC-(CH2)x-COOR4wherein R is3And R4Independently of one another represent C6-C10Alkyl radical, andx is an integer of 2 to 5 and,
(c3)(R5O)3p ═ O, wherein R5Independently of one another represent C6-C12An alkyl group.
Embodiment 10 is the composition of any one of embodiments 1 to 9, wherein the total amount of component (a) relative to the total amount of component (c) is 125:1 to 1:1, preferably 100:1 to 3:2, in each case based on the total weight of the composition.
Embodiment 11 is the composition of any one of embodiments 8-10, wherein the composition comprises component (c) in a total amount of 0.5 to 12 weight percent, preferably in a total amount of 1 to 10 weight percent, based in each case on the total weight of the composition.
Embodiment 12 is the composition of any one of embodiments 1-11, wherein the weight ratio of the total amount of component (a) to the total amount of component (b) is 10:1 to 1:6, and preferably 8:1 to 1:3, in each case based on the total weight of the composition.
Embodiment 13 is the composition of any one of embodiments 8 to 12, wherein the weight ratio of the total amount of component (a) to the total amount of component (c) is 60:1 to 2:1, preferably 40:1 to 3:1, in each case based on the total weight of the composition.
Embodiment 14 is the composition of any of embodiments 1-13, wherein component (d) comprises or consists of propylene glycol monomethyl ether, dipropylene glycol, and/or propylene glycol, and preferably comprises 1-methoxy-2-propanol,
and/or
Component (f) comprises or consists of an alkyl sulfosuccinate salt, preferably C6-C14Alkyl sulfosuccinate monoesters, more preferably lauryl ether-3 sulfosuccinate, in particular disodium lauryl ether-3 sulfosuccinate,
and/or
Component (g) comprises a defoamer, preferably a polydimethylsiloxane oil with silica gel.

Claims (15)

1. A combination comprising or consisting of:
(I) one or more kinds of polyvinyl alcohol(s),
(II) a composition comprising or consisting of:
(a) one or more water-soluble, herbicidally active crop protection agent components (active ingredients of type (a)),
(b) one or more C6-C16Fatty alcohol polyglycol ether sulfate and/or C6-C16Alkyl polyglycoside and/or C10-C18The fatty alkylamine ethoxylates are described as being fatty alkyl amines ethoxylates,
wherein the ratio of the total amount of component (I) to the total amount of component (II) is from 1:100 to 1:5, based on the total weight of the combination.
2. The combination according to claim 1, wherein the total amount of component (I) relative to the total amount of component (II) is from 1:50 to 1:10, based on the total weight of the combination.
3. The combination according to claim 2, wherein the total amount of component (I) relative to the total amount of component (II) is from 1:30 to 1:12, based on the total weight of the combination.
4. The combination according to any one of claims 1-3, wherein the combination is in the form of a kit, co-pack or tank mix.
5. The combination according to any one of claims 1-4, wherein component (I) comprises or consists of a polyvinyl alcohol having a degree of polymerization of 150-.
6. A combination according to any one of claims 1 to 5, wherein component (a) of component (II) comprises or consists of one or more active ingredients selected from: glufosinate and salts thereof, glyphosate and salts thereof, MCPA and salts thereof, dicamba and salts thereof, 2,4-D and salts thereof, and dipropionic acid and salts thereof.
7. A combination according to any one of claims 1 to 6, wherein component (II) is a component(b) Comprises or consists of: one or more C10-C16Fatty alcohol diethylene glycol ether sulfate and/or C with polymerization degree less than 58-C12Alkyl polyglucosides, and/or C having 2 to 10 Ethylene Oxide (EO) units12-C16An alkylamine ethoxylate.
8. The combination according to any one of claims 1-7, wherein the combination or component (II) comprises one or more further components selected from components (c) - (h):
(c) one or more esters selected from (c1) - (c 3):
(c1)R1COOR2wherein R is1Is represented by C5-C13Alkyl and R2Is represented by C6-C14Alkyl radical, wherein R1And R2The total number of carbon atoms taken together is an integer from 14 to 22,
(c2)R3OOC-(CH2)x-COOR4wherein R is3And R4Independently of one another represent C4-C12Alkyl, and x is an integer from 1 to 6,
(c3)(R5O)3p ═ O, wherein R5Independently of one another represent C4-C16Alkyl radical, wherein three R5The total number of carbon atoms taken together is an integer from 18 to 42,
(d) an organic solvent, and a solvent mixture comprising an organic solvent,
(e) the amount of water is controlled by the amount of water,
(f) other surface-active agents which are capable of forming a hydrophilic,
(g) other adjuvants of the preparation can be added into the preparation,
(h) one or more further herbicidally active crop protection agent components and/or herbicide safeners.
9. The combination according to any one of claims 1 to 8, wherein in component (II) the weight ratio of the total amount of component (a) to the total amount of component (b) is from 10:1 to 1:6, preferably from 8:1 to 1: 3.
10. The combination according to any one of claims 1-9, wherein component (c) is present and comprises or consists of one or more esters selected from (c1) - (c 3):
(c1)R1COOR2wherein R is1Is represented by C7-C9Alkyl and R2Is represented by C8-C10Alkyl radical, wherein R1And R2The total number of carbon atoms taken together is an integer from 16 to 20,
(c2)R3OOC-(CH2)x-COOR4wherein R is3And R4Independently of one another represent C6-C10Alkyl, and x is an integer from 2 to 5,
(c3)(R5O)3p ═ O, wherein R5Independently of one another represent C6-C12An alkyl group.
11. A combination according to any one of claims 8 to 10, wherein component (c) is present and the weight ratio of the total amount of component (a) to the total amount of component (c) is from 60:1 to 2:1, preferably the weight ratio of the total amount of component (a) to the total amount of component (c) is from 40:1 to 3:1, in each case based on the total weight of the combination.
12. A combination according to any one of claims 8 to 11, wherein the weight ratio of the total amount of polyvinyl alcohol of component (I) to the total amount of component (c) comprised in the combination is in the range of from 5:1 to 1:5, preferably in the range of from 3:1 to 1:3, more preferably in the range of from 2:1 to 1:2, in each case based on the total weight of the combination.
13. The combination according to any one of claims 1-12, wherein the combination is a tank mix obtainable or obtained by mixing the combination as defined in any one of claims 1-12 with water as component (III), wherein the weight ratio of the total amount of component (III) to the total amount of the combination in the tank mix is from 1000:1 to 10:1, preferably from 500:1 to 25:1, more preferably from 400:1 to 50: 1.
14. A method of controlling undesired plant growth, which comprises applying an effective amount of a combination as defined in any one of claims 1 to 13 to a plant, plant part or cultivation area.
15. Use of a combination as defined in any one of claims 1 to 13 for controlling undesired plant growth.
CN201980059551.6A 2018-07-30 2019-07-23 Compositions comprising PVA and certain herbicides with improved properties Active CN112714612B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP18186336.6 2018-07-30
EP18186336 2018-07-30
US201962811782P 2019-02-28 2019-02-28
US62/811,782 2019-02-28
PCT/EP2019/069796 WO2020025393A1 (en) 2018-07-30 2019-07-23 Combinations containing pva and certain herbicides with improved properties

Publications (2)

Publication Number Publication Date
CN112714612A true CN112714612A (en) 2021-04-27
CN112714612B CN112714612B (en) 2023-03-28

Family

ID=67396960

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201980059551.6A Active CN112714612B (en) 2018-07-30 2019-07-23 Compositions comprising PVA and certain herbicides with improved properties

Country Status (8)

Country Link
US (1) US20210400955A1 (en)
EP (1) EP3829301A1 (en)
CN (1) CN112714612B (en)
AU (1) AU2019314653A1 (en)
BR (1) BR112021001555A2 (en)
CA (1) CA3107831A1 (en)
MX (1) MX2021001198A (en)
WO (1) WO2020025393A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7502263B2 (en) * 2018-07-30 2024-06-18 バイエル・アクチエンゲゼルシヤフト Herbicidal Compositions with Improved Properties

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0476555A2 (en) * 1990-09-15 1992-03-25 Hoechst Schering AgrEvo GmbH Synergistic herbicidal agents
WO1996000010A1 (en) * 1994-06-24 1996-01-04 Zeneca Limited Herbicidal composition
US5491125A (en) * 1988-03-18 1996-02-13 Hoechst Aktiengesellschaft Liquid herbicidal formulations of glufosinate
WO1996022692A1 (en) * 1995-01-24 1996-08-01 Hoechst Schering Agrevo Gmbh Synergistic herbicidal agents based on glufosinates and nitrodiphenyl ethers and their formulations
US20050054532A1 (en) * 2000-05-11 2005-03-10 Jean Kocur Combination of crop protection agents with hydrogen bond-forming polymers
WO2011086115A2 (en) * 2010-01-18 2011-07-21 Basf Se Compound comprising a pesticide and an alkoxylate of 2-propylheptyl amine

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2510839A (en) 1947-12-15 1950-06-06 Standard Oil Dev Co Herbicidal composition
DE3035554A1 (en) 1980-09-20 1982-05-06 Hoechst Ag, 6000 Frankfurt HERBICIDAL AGENTS
DE3719264A1 (en) 1987-06-10 1988-12-29 Hoechst Ag LIQUID PESTICIDAL MIXTURE
AU2992089A (en) 1988-02-22 1989-08-24 Takeda Chemical Industries Ltd. Acrylic acid morpholides, their production and use
EP0407874B1 (en) 1989-07-08 1995-01-18 Hoechst Schering AgrEvo GmbH Defoaming agents for liquid wetting agents and low-foam liquid plant protective agents
CA2100339A1 (en) 1991-01-24 1992-07-25 Erhard John Prill Glyphosate formulations
CA2067060C (en) 1991-04-27 2002-11-26 Jean Kocur Liquid herbicidal compositions
EP0734206B1 (en) 1993-12-17 1999-01-13 Monsanto Company Surfactants providing enhanced efficacy and/or rainfastness to pesticide formulations
CA2224364A1 (en) 1995-06-16 1997-01-03 Monsanto Company Surfactants providing enhanced efficacy and/or rainfastness to pesticide formulations
DE19701123B4 (en) * 1996-02-06 2008-12-24 Basf Se Use of a mixture for the production of pesticidal pesticides
US6713433B2 (en) 1999-08-11 2004-03-30 Monsanto Technology, Llc Coformulation of an oil-soluble herbicide and a water-soluble herbicide
US7441664B2 (en) 2003-05-23 2008-10-28 Pur Water Purification Products Inc. Water treatment devices and cartridges therefor
DE102004026937A1 (en) 2004-06-01 2005-12-22 Bayer Cropscience Gmbh Concentrated aqueous formulations for crop protection
DE102004026935A1 (en) 2004-06-01 2005-12-22 Bayer Cropscience Gmbh Concentrated pesticide dispersions based on water
DE102004026938A1 (en) 2004-06-01 2005-12-22 Bayer Cropscience Gmbh Low-foam aqueous formulations for crop protection
US7842647B2 (en) 2006-02-03 2010-11-30 Bayer Cropscience Lp Stable, concentrated herbicidal compositions
WO2008110274A2 (en) * 2007-03-09 2008-09-18 Syngenta Participations Ag Ternary fungicidal compositions
CN104244711B (en) 2012-04-16 2016-08-24 巴斯夫欧洲公司 Comprise the agricultural formulations of the copolymer of acrylic acid, poly-(aklylene glycol) (methyl) acrylate and (methyl) alkyl acrylate

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5491125A (en) * 1988-03-18 1996-02-13 Hoechst Aktiengesellschaft Liquid herbicidal formulations of glufosinate
EP0476555A2 (en) * 1990-09-15 1992-03-25 Hoechst Schering AgrEvo GmbH Synergistic herbicidal agents
WO1996000010A1 (en) * 1994-06-24 1996-01-04 Zeneca Limited Herbicidal composition
WO1996022692A1 (en) * 1995-01-24 1996-08-01 Hoechst Schering Agrevo Gmbh Synergistic herbicidal agents based on glufosinates and nitrodiphenyl ethers and their formulations
US20050054532A1 (en) * 2000-05-11 2005-03-10 Jean Kocur Combination of crop protection agents with hydrogen bond-forming polymers
WO2011086115A2 (en) * 2010-01-18 2011-07-21 Basf Se Compound comprising a pesticide and an alkoxylate of 2-propylheptyl amine

Also Published As

Publication number Publication date
BR112021001555A2 (en) 2021-04-20
EP3829301A1 (en) 2021-06-09
WO2020025393A1 (en) 2020-02-06
CN112714612B (en) 2023-03-28
US20210400955A1 (en) 2021-12-30
AU2019314653A1 (en) 2021-02-18
MX2021001198A (en) 2021-04-12
CA3107831A1 (en) 2020-02-06

Similar Documents

Publication Publication Date Title
KR101344983B1 (en) Water-based concentrated agricultural pesticide dispersions
JP3152991B2 (en) Liquid herbicide composition
JP4416938B2 (en) Agrochemical formulation
RU2336700C2 (en) Highly-concentrated herbicidal preparation of glyphosate of low viscosity
KR101307012B1 (en) Concentrated aqueous formulations for crop protection
CA2726461C (en) A liquid, homogenous herbicide composition, a method of weed control, a method of production of liquid, homogenous herbicide composition and use of a liquid, homogenous herbicide composition for weed control
JPH10212210A (en) Liquid herbicide
JPH09506615A (en) Surfactants that enhance the efficacy and / or rain resistance of pesticide formulations
JPS63310801A (en) Liquid agricultural drug composition
CN112714612B (en) Compositions comprising PVA and certain herbicides with improved properties
US20020016264A1 (en) Pesticide formulations containing alkoxylated amine neutralized aromaticsulfonic acid surfactants
CN112654246B (en) Herbicidal compositions with improved properties
CN114096154B (en) Stable herbicide composition comprising amine oxide and betaine
EP2448405B2 (en) Aqueous herbicide concentrate
CN116322323A (en) Water-soluble concentrate compositions

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant